Intermediate product for the synthesis ob dyes and process op making



Patented A r. 19,1927.

TgosrAras PATENT orrlcn.

EDUABDKBfiKMENAOHEB, HANS G-UBLEB, OTTO KAISER, 01' BASEL, SWITZERLAND, ASSIGNORS TO SOCIETY OF CHEMICAL INDUSTRY IN" mm, or nasnn, swrrznnnm. rnramnm'rn rnonucr son. was

sni'rnnsrs or nrns' AND raocnss or mxnire Io Drawing.- Application filed m so, 1923, Serial n. 652,856, and in Switzerland September '2, asa.

It hasbeen found that new'int'ermediate products for the synthesis of dyes may be obtained by condensing one-molecular proportion of a cyanuric trihalide with one I molecular proportion of an amine of the aromatic series derived from a hydrocarbon containing at the most 12 -carbon atoms and carrying, on the one hand, at least one mo-' bile atom of hydrogen and, on the other I! hand, at least one strong acid group.

This condensation mayin most cases be 1 carried out in a suitable diluent, audit was surprising to find that as such a' medium water is very appropriate. The course of l the reaction-maybe followed, for instance, 7 by the quantity of the hydrogen halide formed, or by the formation of a precipitate or a elem-solution, or by the disappearance of'the components. I l There are thus obtained new intermediate products of the general formula:

wherein R means an aromatic complex derived from hydrocarbons containing not more than 12 carbon atoms and X hydrogen,

' alkyl or aralkyl, one of the two residues R- and X containing at least one strong acid group. V The newand yellowis powders, they are soluble in solvents yielding colorless to yellow andbrownish solutions and are characterized by g two mobile atoms of halogen at the cyanurlcnucleus.

" The following examples illustrate the present invention without, however, limitmg em Ebcnpla '1;

products are colorless to 17.2 parts of the hydrochloride of m-aminobenzoic acid, and stirred until the m-amino benzoic acid has almost completely disappeared. :The crystallized condensation product thus obtained is 'filtered; crystallized from glacial acetic acid it forms small white needles which melt at about 220 C. with decomposition. The presence of two mobile atoms of chlorine may be traced in the new product. With "the corresponding quantity of hydrochloride of p-aminosalicylic acidin stead of hydrochloride of m-aminobenzoic acid a product is obtained which, crystallized from glacial acetic acid, melts at a temperature higher than 360 C. The presence of two mobile atoms of chlorine and of one group of salicylic acid in the new product may be traced.

E me a r ed, while stirring, with an aqueous solution of 28.5 parts of sodium monobenz'ylaniline sulfonate. After some time the cyanuric chloride has disappeared and a colorless so lution is formed. The .free hydrochloric (5 acid is neutralized and the primary conden sation product obtained from l molecular proportlon of cyanuric chloride with one molecular proportion of monobe laniline sulfonic acid is precipitated by adding oomso mon" salt.- The newproduct forms a y powder, dissolving easily in water, in w ch two mobile atoms of chlorine ma be'tl'aced. It'corresponds very probably with the formula. 86

E sample 3.

18.5 parts of cyanuric chloride are sus pended in iced water and treated, while stirring, witli a"'neutral solution of 24 parts of sodium 1-amino-4-nitro-3-benzene sulfo nate. Into this mixture there are run 50 parts of a solution of sodium carbonate of 10 per cent strength, the whole being kept always feebly acid to congo. The cyanuric chloride disappears gradually and the liquid turns into the form of a jelly. It is stirred untll the nitraniline sulfonic acid has al- "lo t com letely disappeared. The primary indensation product from one molecular proportion of cyanuric chloride and 'one molecular proportion of 1-amino-4-nitro-3- benzene sulfonic acid is then thrown out nith chloride of potassium. The product thus obtained forms a fine, crystallized, almost colorless precipitate freely soluble in water; its aqueous solution turns to yellow by addition of alkalies.

Example 4.

18.5 arts of cyanuric chloride am suspended in 500 parts of cold water and treated with an aqueous solution of 19.6 parts of the sodium salt of sulfanilic acid. After some time the sulfanilic acid has almost completely disappeared and the almost colorless and crystallized primary condensation product thus obtained from 1 molecular proportion of cyanuric chloride and one molecular proportion of sulfanilic acid is filtered and dried. It corresponds very probably with the formula N/ N soa t ln If the 19.5 parts of the sodium salt of sulfanilie acid are replaced by the corresponding quantities of the sodium salts of 1- amino-4-acetylamino-3-benzene sulfonic acid or of l-aminoi-acetylaminonaphthalene7- sulfonic acid, similar primary condensation products are obtained, which form light powders containing, on the one hand, two mobile atoms of chlorine and, on the other hand, one acetylamino group.

Emample 5.

To a fine suspension of 18.5 parts of cyanuric chloride in 500 parts of water there is added slowly and at a low temperature a solution of 18.8 arts of 1 :8-phenylendiam ine-e-sulfonic acid and 5.3 parts of sodium carbonate in 100 partsof water. As soon as the cyanuric chloride has disappeared, the

' precipitate is filtered. The grey'powder thus obtained represents the primary condensation product from 1 molecular proportion of 1:3-phenylenediamineA-sulfonic acid and 1 molecular pro ortion of cyanuric chloride. It correspon s very probably with the formula Due to its two mobile atoms of chlorine the product is capable of many transformations.

Example 6'.

A fine suspension of 18.5 parts of cyanuric chloride in 1000 parts of Water is slightly acidified with hydrochloric acid and treated afterwards, while stirring, at 0 C., with a solution of 26.2 parts of sodium 2:5-aminonaphthol-7-sulfonate in 500 parts of water, the liquid being kept feebly acid by addition of a solution of sodium carbonate (5.3 parts in all). The clear solution thus obtained contains the condensation product of 1 molecular proportion of cyanuric chloride and 1 molecular proportion of 2:5aminonaphthol-7- sulfonic acid which may be thrown out by means of common salt.

The product is characterized by the fact that by addition of alkalies or alkali metal carbonates it is transformed into a product which no longer reacts with diazo-compounds.

Example 7'.

18.5 parts of cyanuric chloride are dissolved by gently warming in 50 parts of acetone, and the solution is poured, while vigorously stirring, into 500 parts of water. Into the suspension of cyanuric chloride thus obtained there is run a-solution of 31.9 parts of 1 8-aminonaphthol-3 fi-disulfonic acid in 13.3 parts of caustic soda solution of 30 per cent strength and 150 parts of water. The cyanuric chloride dissolves very rapidly, and the condensation product from 1 molecular proportion of cyanuric chloride and one molecular proportion of 1 8-aminonaphthol- 3:6-disulfonic acid is separated from the solution by addition of common salt. The new product, still containing two mobile atoms of chlorine, forms in the dry state a white powder soluble in water much more easily than the 1:8-aminonaphthol-3:6-disulfonic acid. It is not diazotizable and its alkaline solutions have no fluorescence in contradistinction to those of the above parent'materiai. The new product. corresponds very probably with the formula 1 no n nlk t qn Other aminona hthols, as for example,

' the 2:8-aminonap thol-6-sulfonic acid, the

1 8-aminonaphtholl-sulfonic acid, the 1 5' -aminonaphthol-7-sulfonic acid, and the like,

react in the same manner as the '2 5-aminonaphthol-7-sulfonic acid and the 1 S-aminonaphthol-3z6-disulfonic acid. v

What we claim is: o y 1. The herein describedprocess of making new intermediate productsfor the synthesis -.1of dyes, which consists in condensing one molecular proportion of a cyanuric trihalide new intermediate products for the synthesis of dyes, which consists in condensing one molecular proportion of a cyanuric trihalide with one molecular proportlon of a primary ing carried out in water.

amine of the aromatic series which contains at least one Sulfo group and which is derived from a hydrocarbon having-not more than12 carbon atoms, the condensation be- 3. As new intermediate products for the synthesis of dyes, the herein described new compounds of the general'formula:

wherein R means an aromatic complex derived from hydrocarbons havmg not more nucleus.

signed than carbon atoms andXh dro en l a y anfl or arallgyl, one of the two residues a contaimng'at least one strong acid group,

' which products are colorless to gray and yellowish powders, dissolvlng in-solvents yieldmg colorless to yellow and brownish solutions, and which-are characterized by two mobile atoms of halogen at the cyanuric 4. As new intermediate products for the synthesis of dyes, the herein described new compounds of'the general formula:

'- Halogen wherein R means an aromatic complex der1ved:-from hydrocarbons having not more than 12 carbon atoms, and X hydrogen, an or aralkyl, one of the two residues R and containing at least one sulfo group, which products are colorless to 'ay and yellowish powders, dissolving'in so vents yielding col orless to, yellow and brownish solutions,

and which are characterized by two mobile atoms of halogen at the cyanuric nucleus. 5. As-new intermediate products for the synthesis of dyes the herein described new compounds of theogeneral formula:

'wherein R means an aromatic complex 'derived from hydrocarbons having-not more than 12 carbon atoms and at least one sulfo group, 'which products are colorless t o gray and yellowish powders, dlssolving 1n solvents. yielding, colorless to yellow and brownish solutions, and which are characterized by two mobile atoms of halogen at a the cyanuric nucleus.

- In witness whereof we have hereunto our names this ,6th day of July 1923.

HERMANN FRITZSCHE. 1 I, EDUARD KRUh/IMENACHLER'.

HANS GUBLER.

OTTO KAISER. 

